Tunability of the optical absorption in small silver cluster-polymer hybrid systems

TL;DR

This study uses time-dependent density-functional theory to show how the optical absorption of silver cluster-polymer hybrids can be tuned across the visible spectrum based on cluster electron count and structure.

Contribution

It provides the first theoretical analysis of how polymer interactions influence the spectral properties of small silver clusters.

Findings

Absorption spectra depend heavily on polymer structure.

Odd-electron clusters can be tuned into the visible range.

Even-electron clusters have a shifted absorption edge up to 4.5 eV.

Abstract

We have calculated the absorption characteristics of different hybrid systems consisting of Ag, Ag2 or Ag3 atomic clusters and poly(methacrylic acid) (PMAA) using the time-dependent density-functional theory. The polymer is found to have an extensive structural-dependency on the spectral patterns of the hybrid systems relative to the bare clusters. The absorption spectrum can be `tuned' to the visible range for hybrid systems with an odd number of electrons per silver cluster, whereas for hybrid systems comprising an even number of electrons, the leading absorption edge can be shifted up to about 4.5 eV. The results give theoretical support to the experimental observations on the absorption in the visible range in metal cluster-polymer hybrid structures.